CN103918086A - Durable polyolefin adhesive material for solar modules - Google Patents

Durable polyolefin adhesive material for solar modules Download PDF

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Publication number
CN103918086A
CN103918086A CN201280054116.2A CN201280054116A CN103918086A CN 103918086 A CN103918086 A CN 103918086A CN 201280054116 A CN201280054116 A CN 201280054116A CN 103918086 A CN103918086 A CN 103918086A
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film
film described
alpha
olefin copolymer
low
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CN103918086B (en
Inventor
R·M·拉萨尔
J·M·詹尼恩
J·G·莱尼尔特
B·厄尔多甘-豪格
R·S·克洛
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

This disclosure generally relates to films capable of use in electronic device modules and to electronic device modules including such films. The disclosure also generally relates to materials for use in such films.

Description

For the durable polyolefin-based adhesive material of solar module
Technical field
The present invention relates generally to the film that can be used in photovoltaic solar cell assembly, and relates to the photovoltaic solar cell assembly that comprises this type of film.The present invention also relates generally to the material for this type of film.
Background technology
Three kinds of commercially available acquisitions of essential structure of photovoltaic solar cell assembly.The first structure of solar module 10 is illustrated in Fig. 1 and comprises the photovoltaic cell 20 embedding in encapsulation piece 30.The front and back setting of panel 40, the 50 contiguous encapsulation pieces of two blocks of glass (or other suitable material).Encapsulation piece is protected frangible solar cell and battery is adhered to front and back glassy layer.Conventionally, this of solar module is configured on the both sides of solar cell and includes encapsulation piece.This can be for example by comprising that front encapsulated layer (being set to towards the sun) and back side encapsulated layer (being set to away from the sun) realize.It is high radioparent that front encapsulated layer is preferably, and back side encapsulated layer is without the transmittance with same degree.This structure of photovoltaic solar cell assembly is roughly described in the open No.2008/0078445 of for example United States Patent (USP).
The second structure of solar module 60 is illustrated in Fig. 2 and comprises the photovoltaic cell 70 being arranged between single encapsulated layer 80 and back lining materials 90 (being generally glass).Solar panel 60 also comprises the protective layer 100 of contiguous encapsulated layer 80.As shown in Figure 2, the design of this solar panel comprises front encapsulation piece and without back side encapsulation piece.This structure of photovoltaic solar cell assembly is roughly described in the open No.2008/0078445 of for example United States Patent (USP).
The third structure of solar module 110 is illustrated in Fig. 3 and comprises the photovoltaic cell 120 being arranged between single encapsulated layer 130 and protective layer 150.Solar panel 110 also comprises the back sheet 140 (being generally glass) of contiguous encapsulated layer 130.As shown in Figure 3, the design of this solar panel comprises back side encapsulation piece and without front encapsulation piece.This structure of photovoltaic solar cell assembly is for example roughly described in U.S. Patent No. 5,248,349.
Summary of the invention
Some exemplary packet sealings comprise ethylene vinyl acetate (EVA) and crosslinking agent (for example peroxide).The present inventor recognizes, although crosslinked EVA film usually has high strength, they can exist following problem: relatively high moisture-vapor transmission, flavescence and may corroding because discharging acetic acid.
Some example package layers comprise the resin being clamminess.This sticky work property is a shortcoming, because it can cause at " obstruction " processed in rolled article or general film storage or processing procedure.Therefore, present inventor recognizes, wishes to produce the film not more being clamminess or uses the resin not more being clamminess.
Solar panel working temperature is through measuring up to 110 DEG C.Present inventor recognizes, the encapsulated membranes that comprises thermoplastic adhesives can deliquescing under this high temperature, thereby causes panel creep and may cause photovoltaic cell short circuit.These encapsulated membranes also may be easy to occur UV-induced fault, thereby must comprise a large amount of ultra-violet absorbers, and this has limited the amount can be used for for the incident light of solar cell energy supply.The present inventor also recognizes, resinoid can exist extrudes the slower problem of process velocity, thereby manufacturing cost is increased.
Therefore, need to make one or more the incidence in creep, contraction, printing opacity, flavescence, corrosivity and layering to be down to minimum encapsulated membranes and the material that maintains simultaneously or improve film machinability and manufacturing cost.The present inventor found to provide in performance, cost and the machinability of improvement at least one encapsulated membranes, for the material of this type of film and comprise the solar module of this type of film and material.
In one exemplary embodiment, a kind of film that can be used in photovoltaic solar cell assembly comprises: have DSC peak value fusing point and be less than or equal to the first low-crystalline ethylene/alpha olefin copolymer of 50 DEG C; There is the second low-crystalline ethylene/alpha olefin copolymer that DSC peak value fusing point is greater than 50 DEG C; Silane; With one or more crosslinking agents.
In another exemplary embodiment, a kind of film that can be used in photovoltaic solar cell assembly comprises: have the first polyolefin that DSC peak value fusing point is less than or equal to 50 DEG C; There is the second polyolefin that DSC peak value fusing point is greater than 50 DEG C; Silane; With one or more crosslinking agents; Wherein be exposed to " 85/85 durability test " transmission % on average at least 90% in the wave-length coverage at 400-1100nm after 1000 hours.
In certain embodiments, described polyolefin is ethylene/alpha-olefin copolymer.In certain embodiments, the alpha-olefin part of described ethylene/alpha-olefin copolymer comprises four or more carbon.In certain embodiments, described ethylene/alpha-olefin copolymer is low-crystalline ethylene/alpha olefin copolymer.In certain embodiments, the DSC peak value fusing point of described low-crystalline ethylene/alpha olefin copolymer is less than or equal to 50 DEG C.In certain embodiments, described low-crystalline ethylene/alpha olefin copolymer is butylene alpha-olefin.In certain embodiments, described film is the low-crystalline ethylene/alpha olefin copolymer that is greater than 70 % by weight.In certain embodiments, described silane is unsaturated alkoxy silane.In certain embodiments, described unsaturated alkoxy silane is alkyl acrylate TMOS.In certain embodiments, described one or more crosslinking agents are the one in hot curing crosslinking agent and photocured cross-linked dose.In certain embodiments, described hot curing crosslinking agent is peroxide.In certain embodiments, described film also comprises auxiliary agent.In certain embodiments, described film also comprises other resin.In certain embodiments, described other resin is other low-crystalline ethylene/alpha olefin copolymer.In certain embodiments, described film also comprises the hindered amine as light stabilizer that ultraviolet cutoff value is 310nm (HALS).In certain embodiments, be exposed to 85/85 durability test after 1000 hours in the wave-length coverage at 400-1100nm the average transmission % of described film be at least 90%.In certain embodiments, longitudinal contraction rate measured value is less than 10%.In certain embodiments, the gel fraction of described film is less than 20%.In certain embodiments, the gel fraction of described film is less than 5%.In certain embodiments, described film comprises multiple layers.In certain embodiments, described film is in solar module.
Brief description of the drawings
The detailed description of considering by reference to the accompanying drawings following each embodiment of the present invention can comprehend the present invention, wherein:
Fig. 1 is the profile of the prior art photovoltaic solar cell assembly of a type.
Fig. 2 is the profile of the prior art photovoltaic solar cell assembly of a type.
Fig. 3 is the profile of the prior art photovoltaic solar cell assembly of a type.
Accompanying drawing may not be drawn in proportion.Should be appreciated that the parts that are used to indicate the label of parts and are not intended to limit same numeral in another accompanying drawing in given accompanying drawing.
Embodiment
In the following detailed description, can be with reference to forming one group of a part of accompanying drawing of this explanation, and wherein by diagram, some specific embodiments are shown.Should be appreciated that and do not departing from the scope of the present invention or spirit in the situation that, imagining other embodiment and can modify.Therefore, following embodiment does not have restrictive, sense.
The application relates generally to the film that can be used in solar module.Film of the present invention can be used for the photovoltaic solar cell assembly of any type, comprises example any solar module as described in the background art.In one exemplary embodiment, a kind of film that can be used in photovoltaic solar cell assembly comprises: have DSC peak value fusing point and be less than or equal to the first low-crystalline ethylene/alpha olefin copolymer of 50 DEG C; There is the second low-crystalline ethylene/alpha olefin copolymer that DSC peak value fusing point is greater than 50 DEG C; Silane; With one or more crosslinking agents.In another exemplary embodiment, a kind of film that can be used in photovoltaic solar cell assembly comprises: have the first polyolefin that DSC peak value fusing point is less than or equal to 50 DEG C; There is the second polyolefin that DSC peak value fusing point is greater than 50 DEG C; Silane; With one or more crosslinking agents; Wherein be exposed to " 85/85 durability test " transmission % on average at least 90% in the wave-length coverage at 400-1100nm after 1000 hours.
polyolefin
In certain embodiments, polyolefin is one or more in EVA, high density polyethylene (HDPE), ionomer, polystyrene and polyvinyl butyral resin.
In certain embodiments, polyolefin is ethylene/alpha-olefin copolymer.As used herein, term " ethylene/alpha-olefin copolymer " refers to and comprises the polymer that reacts the class hydrocarbon that (aggregating into low molecular weight product) make by ethene with the catalytic oligomerization of linear alpha-olefin monomer.Described ethylene/alpha-olefin copolymer can for example be used such as the single-site catalysts of metallocene catalyst or such as the multicenter catalyst of Z-N (Ziegler-Natta) catalyst and Philips (Phillips) catalyst and prepare.Described linear alpha-olefin monomer is generally 1-butylene or 1-octene, but can be in the scope of C3 to C20 straight chain, side chain or ring-type alpha-olefin.Described alpha-olefin can be side chain, but only side chain at least when the α position in two keys can, such as 3-Methyl-1-pentene.The example of C3-C20 alpha-olefin comprises propylene, 1-butylene, 4-methyl isophthalic acid-butylene, 1-hexene, 1-octene, 1-dodecylene, tetradecene, cetene and 1-vaccenic acid.Described alpha-olefin can also contain circulus, such as cyclohexane or pentamethylene, thereby produces the alpha-olefin such as 3-cyclohexyl-1-propylene (allyl cyclohexane) and vinyl cyclohexane.Although be not the alpha-olefin in the classical meaning of this term, for purposes of the present invention, be alpha-olefin and can use such as some cyclic olefin of norborene and associated olefinic.Similarly, for purposes of the present invention, styrene and associated olefinic thereof (for example AMS) are alpha-olefin.But for purposes of the present invention, acrylic acid and methacrylic acid and ionomer separately thereof and acrylate and methacrylate are not alpha-olefins.Exemplary ethylene/alpha-olefin copolymer comprises Ethylene/1-butene, ethene/1-octene, Ethylene/1-butene/1-octene, ethylene/styrene.Polymer can be block polymer or atactic polymer.Low-crystalline ethylene/the alpha olefin copolymer of exemplary commercially available acquisition comprises the resin of selling by following trade name: purchased from " ENGAGE " Ethylene/1-butene and ethene/1-octene copolymer and " FLEXOMER " ethene/1-hexene copolymer of Dow Chemical (Dow Chemical Co.); And evenly side chain, the ethylene/alpha-olefin copolymer of straight chain substantially, such as " TAFMER " purchased from mitsui petrochemical industry Co., Ltd (Mitsui Petrochemicals Company Limited) with purchased from " EXACT " of Exxon Mobil Corporation (ExxonMobil Corp.).As used herein, term " copolymer " refers to the polymer of being made up of at least 2 monomers.
In some these type of embodiment, the alpha-olefin part of ethylene/alpha-olefin copolymer comprises four or more carbon.In certain embodiments, ethylene/alpha-olefin copolymer is low-crystalline ethylene/alpha olefin copolymer.As used herein, term " low crystallization " means to be less than the degree of crystallinity (according to disclosed method in ASTM F2625-07) of 50 % by weight.In certain embodiments, described low-crystalline ethylene/alpha olefin copolymer is butylene alpha-olefin.In certain embodiments, the alpha-olefin of described low-crystalline ethylene/alpha olefin copolymer has 4 or more carbon.
In certain embodiments, described film comprises and has DSC peak value fusing point and be less than or equal to the first low-crystalline ethylene/alpha olefin copolymer of 50 DEG C and have the second low-crystalline ethylene/alpha olefin copolymer that DSC peak value fusing point is greater than 50 DEG C.As used herein, term " DSC peak value fusing point " means to be determined as by DSC the fusing point (10 °/min) of the peak value with maximum DSC TG-AUC under nitrogen blowing.
In certain embodiments, described film comprises the low-crystalline ethylene/alpha olefin copolymer that is greater than 35 % by weight.In some embodiment that comprise the first low-crystalline ethylene/alpha olefin copolymer and the second low-crystalline ethylene/alpha olefin copolymer, total low-crystalline ethylene/alpha olefin copolymer content (, comprise the first and second low-crystalline ethylenes/alpha olefin copolymer both) is greater than the low-crystalline ethylene/alpha olefin copolymer of 35 % by weight.In certain embodiments, described film is the low-crystalline ethylene/alpha olefin copolymer that is greater than 50 % by weight.In some embodiment that comprise the first low-crystalline ethylene/alpha olefin copolymer and the second low-crystalline ethylene/alpha olefin copolymer, total low-crystalline ethylene/alpha olefin copolymer content (, comprise the first and second low-crystalline ethylenes/alpha olefin copolymer both) is greater than the low-crystalline ethylene/alpha olefin copolymer of 50 % by weight.In certain embodiments, described film is the low-crystalline ethylene/alpha olefin copolymer that is greater than 70 % by weight.In some embodiment that comprise the first low-crystalline ethylene/alpha olefin copolymer and the second low-crystalline ethylene/alpha olefin copolymer, total low-crystalline ethylene/alpha olefin copolymer content (, comprise the first and second low-crystalline ethylenes/alpha olefin copolymer both) is greater than the low-crystalline ethylene/alpha olefin copolymer of 70 % by weight.
In certain embodiments, described film comprises other vistanex.Exemplary other resin comprises for example low-crystalline ethylene/alpha olefin copolymer, HDPE and polystyrene.In the embodiment that described other resin is low-crystalline ethylene/alpha olefin copolymer therein, for example, two kinds of copolymers DSC peak value fusing point separately can for example be less than 50 DEG C and be greater than 50 DEG C.In an alternative exemplary embodiment, a kind of DSC peak value fusing point of low-crystalline ethylene/alpha olefin copolymer can be less than 50 DEG C, and the DSC peak value fusing point of another kind of low-crystalline ethylene/alpha olefin copolymer can be greater than 55 DEG C or be greater than 60 DEG C or be greater than 65 DEG C or be greater than 70 DEG C or be greater than 75 DEG C.In another exemplary embodiment, a kind of DSC peak value fusing point of low-crystalline ethylene/alpha olefin copolymer can be greater than 50 DEG C, and the DSC peak value fusing point of another kind of low-crystalline ethylene/alpha olefin copolymer can be less than 45 DEG C or be less than 40 DEG C or be less than 35 DEG C.In an alternative exemplary embodiment, the one in two kinds of low-crystalline ethylene/alpha olefin copolymers is that ethylene/butylene copolymers and another one are ethylene/octene.
silane
Exemplary silane for film of the present invention comprises the silane that for example comprises following group: ethylenic unsaturated alkyl group (such as for example vinyl, pi-allyl, isopropenyl, cyclobutenyl, cyclohexenyl group or γ-(methyl) acryloxy allyl group) and hydrolyzable groups (such as for example methoxyl group, ethyoxyl, formyloxy, acetoxyl group, propionyloxy, alkyl, virtue amino, alkyl oxygen base or alkyl amino group).In some exemplary embodiments, described silane is unsaturated alkoxy silane.In some exemplary embodiments, described unsaturated alkoxy silane is acrylic silane.Some examples comprise vinyltrimethoxy silane, vinyltriethoxysilane and 3-(methyl) acryloxy propyl trimethoxy silicane.The example of commercially available acquisition comprises " SILQUEST A174 " and " SILQUEST A171 ".
The amount of silane is generally at least about 0.05%, and for example 0.1%, for example 0.5%, for example 1.0%, for example 2.0%, for example 10.0%, or even for example 10.0%.
crosslinking agent
Film of the present invention comprises one or more crosslinking agents.Exemplary crosslinking agent comprises for example thermal cross-linking agent and photocrosslinking agent.
Some exemplary hot crosslinking agents comprise for example peroxide.Some exemplary peroxide comprise for example diacyl peroxide (such as for example dilauroyl peroxide and didecanoyl peroxide), alkyl super-acid ester (such as for example peroxidating (2 ethyl hexanoic acid) tert-butyl ester), cross ketal (such as for example 1, 1-bis-(tert-butyl hydroperoxide)-3, 3, 5-trimethyl-cyclohexane or 1, 1-bis-(tert-butyl hydroperoxide) cyclohexane), dialkyl peroxide is (such as for example tert-butyl peroxide isopropylbenzene, di-tert-butyl peroxide and cumyl peroxide), C-free radical donor is (such as for example 3, 4-dimethyl-3, 4-diphenyl hexane and 2, 3-dimethyl-2, 3-diphenyl butane) and azo-compound (such as for example 2, 2'-azo two (2-acetoxy-propane)).Other exemplary azo-compound is included in U.S. Patent No. 3,862, and 107 and No.4, those described in 129,531.The peroxide of some exemplary commercially available acquisitions for example comprises " LUPEROX TBEC ", " LUPEROX231 " and " LUPEROX P ".Can use the mixture of two or more crosslinking agents.
The amount of crosslinking agent can change, but minimum is enough to provide the crosslinked of required scope.In certain embodiments, described film comprises at least about 0.05%.In certain embodiments, described film comprises at least about 0.5%.In certain embodiments, described film comprises at least about 1.0%.In certain embodiments, described film comprises at least about 2.0%.In certain embodiments, described film comprises at least about 5.0%.
plasticizer
The preferred plasticizer that is used for film as herein described is not variable and/or makes those plasticizer of the crosslinked polymer in film.Can improve and extrude process velocity and reduce film shrinkage for the plasticizer of film as herein described, at the temperature between between approximately 100 DEG C and 200 DEG C, increase storage modulus (creep resistance) simultaneously.Preferably, this type of plasticizer is not also substantially clamminess under normal process or storage temperature.In some exemplary embodiments, at 20 DEG C, be liquid for the described plasticizer of film.In some exemplary embodiments, described plasticizer does not serve as tackifier.
In some exemplary embodiments, described plasticizer is nonpolar.As used herein, term " nonpolar plasticizer " means to increase plasticity, fluidity or the mobility of low-crystalline ethylene/alpha-olefine polymers and has the non-polar additives that is less than 10,000 MW of measuring by ASTM D6474.As used herein, nonpolar plasticizer does not for example comprise common polarity polyvinyl chloride (PVC) plasticizer, for example, such as ditridecyl phthalate (diethyl phthalate, dibutyl phthalate, dioctyl phthalate); Or other polarity ester plasticiser, such as trimellitate, adipate ester, sebacate, maleate, citrate or benzoic ether.The example of nonpolar plasticizer comprises for example ethylene/alpha-olefin copolymer and C4-C10 polyolefin homopolymer.In some exemplary embodiments, described nonpolar plasticizer can be selected from ethylene/alpha-olefin copolymer and C4-C10 polyolefin homopolymer.
The nonpolar plasticizer of exemplary commercially available acquisition comprises can be from (the ExxonMobil Chemical of Louisiana Baton Rouge ExxonMobil Chemical with trade name " SPECTRASYN ", Baton Rouge, LA) commercially available, can be from (the Sonneborn Refined Products B.V. of Amsterdam, the Netherlands Sohne this refinement company with trade name " KAYDOL " white mineral oil, Amsterdam, the Netherlands) commercially available, can be from (the Ineos Oligomers of Li Ge city, Texas Ineos oligomer company with trade name " INDOPOL " polybutene, League City, TX) commercially available and can be from (the Lion Copolymer of Louisiana Baton Rouge lion chemical company with trade name " TRILENE " ethylene, propylene (EP) or EPDM copolymer, Baton Rouge, LA) commercially available those.
The Tg of described nonpolar plasticizer can be less than-50 DEG C, for example, be less than-55 DEG C, for example, be less than-65 DEG C, for example, be less than-70 DEG C, or is even for example less than-75 DEG C.The DSC peak value fusing point of described plasticizer can be less than 80 DEG C, for example, be less than 60 DEG C, for example, be less than 40 DEG C or be even for example less than 20 DEG C.In one embodiment, described plasticizer is liquid at 20 DEG C.
In some exemplary embodiments, substantially do not exist such as the conventional plasticizer that is usually used in gathering (vinyl chloride).As used in this section, term " does not substantially exist " and means deliberately these compounds not to be added in composition, and if exist, comprises below 0.5 % by weight of total film composition.
Specifically, plasticizer such as phthalic acid ester, adipate ester, trimellitate, polyester and as at for example US3,318,835, US4,409,345, disclosed other functionalized plasticizer and PLASTICS additive 499-504 (Geoffrey Pritchard in WO02/31044Al, ed., Chapman & Hall1998 (Geoffrey Pritchard edits, Cha Puman and Hall publishing house, 1998)) substantially do not exist.
The amount of plasticizer is generally at least about 0.5%.In certain embodiments, the amount of plasticizer is at least about 1.0%.In certain embodiments, the amount of plasticizer is at least about 2.0%.In certain embodiments, the amount of plasticizer is at least about 5.0%.In certain embodiments, the amount of plasticizer is at least about 10.0%.In certain embodiments, the amount of plasticizer is at least about 20.0%.
additive
In some exemplary embodiments, film of the present invention comprises auxiliary agent.Exemplary auxiliary agent comprises for example radical crosslinking auxiliary agent (promoter or coinitiator).The example of this analog assistant comprises acrylate and methacrylate, allyl alcohol derivative and the low molecular weight polybutadiene of polyfunctional vinyl monomer and polymer, cyanacrylate, trimethylol-propane trimethacrylate, divinylbenzene, polyalcohol.Sulfur-crosslinked promoter comprises benzothiazole based bisulfide, 2-mercaptobenzothiazole and TMTT tetramethyl thiuram tetrasulfide.
In some exemplary embodiments, described film also comprises one or more ultra-violet absorbers.Ultra-violet absorber absorbs light and thereby can protect polymeric material and/or solar cell.Some exemplary ultra-violet absorbers comprise for example triazines, benzotriazole, hydroxy benzophenone ketone, hydroxyphenyltriazinuv class, benzoic ester and the mixture of two or more thereof.In some exemplary embodiments, film of the present invention comprises 0.01% ultra-violet absorber.In some exemplary embodiments, film of the present invention comprises 0.1% ultra-violet absorber.In some exemplary embodiments, film of the present invention comprises 0.5% ultra-violet absorber.In some exemplary embodiments, film of the present invention comprises 1% ultra-violet absorber.
The film that comprises ultra-violet absorber has " UV cutoff ".As used herein, term " UV cutoff " refers to the wavelength transmittance of film and means this film by all UV light being substantially blocked in below specified wavelength threshold value.In certain embodiments, " the UV cutoff " of film of the present invention is respectively 310nm, 350nm and 380nm.This type of film can for example comprise respectively " TINUVIN622 " HALS, " CHIMASSORB81 " ultra-violet absorber or " TINUVIN460 " ultra-violet absorber lower than 0.5%.
In some exemplary embodiments, described film comprises one or more hindered amine as light stabilizer (" HALS ").HALS is light stabilizer and non-absorbent and removes free radical by producing nitroxyl free radical.In certain embodiments, comprise HALS but not ultra-violet absorber can allow more luminous energy to enter solar cell.Some exemplary HALS comprise for example cyclammonium class, the second month in a season, uncle, acetylation, N-oxyl N-oxyl that replace, that hydroxyl replaces cyclammonium class that replace or other replacement; the cyclammonium class of described replacement further characterizes by sterically hindered degree, described sterically hindered conventionally because replace aliphatic group or close on amine official can carbon atom on group due to.
In some exemplary embodiments, film of the present invention comprises 0.01% HALS.In some exemplary embodiments, film of the present invention comprises 0.1% HALS.In some exemplary embodiments, film of the present invention comprises 0.5% HALS.In some exemplary embodiments, film of the present invention comprises 1% HALS.
Other additive comprises for example pigment, such as carbon black and titanium dioxide; Inorganic filler, such as talcum powder, pyrogenic silica, precipitated silica, barium sulfate and calcium carbonate; Crosslinking agent; Antioxidant; Coking inhibitor; Fire retardant; And crosslinking catalyst, such as organo-tin compound, for example di-n-butyltin dilaurate.Other suitable catalyst comprises (for example) titanium compound and metal alkoxide, for example, and aluminium isopropoxide and zirconium iso-propoxide.
Film of the present invention can use the known technology manufacture in film shaping field, is included in and on release liner, is coated with and solidifies and extrusion coated.In certain embodiments, described film can be used as adhesive and can be exposed to further processing, for example heat and pressure.In certain embodiments, described film is extruded.In some exemplary embodiments, film of the present invention is sent with the form of film.In some exemplary embodiments, film of the present invention comprises standard mat surface.In some exemplary embodiments, film of the present invention is provided on release liner.
In certain embodiments, described film comprises multiple layers.In an illustrative embodiments, film of the present invention comprises three or more layers.In an illustrative embodiments therein, described one or more crosslinking agents, silane and/or polyolefin are in different layers.For example, described one or more crosslinking agents can be substantially or completely in central core and polyolefin and silane can be in skin.In certain embodiments, film of the present invention can be used as flexible polyolefin backboard and/or top board.
Film of the present invention can be used for solar module.Described solar module can have any type known in the art.In certain embodiments, described film or composition can be used as the adhesive of solar module herein.In this type of purposes, described film or composition can be described as " assembly adhesives ", because they are for assembling at least two elements of solar module keep together.
For example, in some exemplary embodiments (rete is incorporated on solar cell those), low-gel content may be preferred, provide better adhesion and flexibility because there is the film of low-gel content, until be cured to higher gel content under higher temperature.In some exemplary embodiments, as measured by ASTM D2765-11, the gel fraction of cured films is less than 20%.In some exemplary embodiments, as measured by ASTM D2765-11, the gel fraction of cured films is less than 10%.In some exemplary embodiments, as measured by ASTM D2765-11, the gel fraction of cured films is less than 5%.In some exemplary embodiments, in the time measuring according to ASTM D2765-11, the gel content after being cross-linked is at least 40%.In some exemplary embodiments, in the time measuring according to ASTM D2765-11, the gel content after being cross-linked is at least 50%.In some exemplary embodiments, in the time measuring according to ASTM D2765-11, the gel content after being cross-linked is at least 60%.In some exemplary embodiments, in the time measuring according to ASTM D2765-11, the gel content after being cross-linked is at least 70%.
In the wave-length coverage of 400-1100nm, the average transmission % of film of the present invention is at least 90%.This allows film of the present invention and composition to be used as front encapsulated membranes.In certain embodiments, be exposed to 85/85 durability test after 1000 hours in the wave-length coverage at 400-1100nm the average transmission % of film of the present invention be at least 90%.In certain embodiments, the longitudinal contraction rate measured value of described film is less than the not longitudinal contraction rate measured value of the film of plasticizer-containing.In certain embodiments, the storage modulus measured value of the film that the storage modulus measured value of described film at 100 DEG C is greater than plasticizer-containing not at 100 DEG C.In certain embodiments, the storage modulus measured value of the film that the storage modulus measured value of described film at 150 DEG C is greater than plasticizer-containing not at 150 DEG C.
Encapsulated membranes of the present invention and material show at least some in following advantage compared to current available encapsulated membranes: the incidence of creep, contraction, flavescence, corrosion and layering is down to minimum, maintains simultaneously or improve light transmittance, film machinability and manufacturing cost.Further by following instance, additional advantage of the present invention and embodiment are described, but the concrete material of recording in these examples and amount thereof and other conditions and details all should not be interpreted as to improper restriction of the present invention.Unless otherwise indicated, otherwise in these examples, all percentage, ratio and ratios are all by weight.
example
comparative example 1 & 2 (being referred to herein as " CE1 " and " CE2 ") and example 1-3 are (herein in be called " EX1 ", " EX2 " and " EX3 ")
Listed composition and then mixture at room temperature being soaked 24 hours in premixed table 1.Follow at 200 DEG C at Brabender (model EPL V5502, derive from brabender instrument company (C.W.Brabender Instruments, Inc.)) in by gained mixture processing 10 minutes and use Carver Hydraulic press (model 3925) to be depressed into the thickness of 18 mils.
table 1. is filled a prescription
Attention: total copolymer adds to 100 and the umber (pph) of all other compositions based on every hundred parts of copolymers meter
sticky work property
The film (for example, two CE1 films, two CE2 films, two EX1 films, two EX2 films and two EX3 films) of two 18 identical mil thick forces together with light pressure with hand, to determine whether they cling each other.If these films stick together, this film type is considered as " being clamminess " so.Comparative example 1 (CE1) is clamminess, and all other examples (CE2, EX1, EX2 and EX3) are not clamminess.
aging adhesion test
Also dry with the two sides of the clean 6 inches × 6 inches of square float glasses of isopropyl alcohol.This square float glass has tin face (having fuzzy blue aura under UV light) and non-tin face.From the patty thing of formation described above, cut the membrane sample (CE1, CE2, EX1, EX2 and EX3) of 6 square inches × 18 mil thick.The release liner of 0.75 inch × 6 inches of a slices (the 2 mil polyester release liners that Mitsubishi (Mitsubishi) is sold) is placed on an edge between glass and encapsulation piece to help promptly as " starting " inserted sheet.The solar energy backboard of 6 inches × 6 inches of a slices of cutting (can trade name " 3M SCOTCHSHIELD17 " commercially available from Sao Paulo, Minnesota State 3M company (3M, St.Paul, MN)) is also arranged on membrane sample with smooth EVA face.Then at 150 DEG C in the photovoltaic module laminator LM-50X50-S being sold by NPC group (NPC Group) by laminated this structure 15 minutes.
By sample be placed in through preheating and through pre-moisturized " CASCADE SE-1000-6-6 " environmental chamber (can from state of Michigan Huo Lanre survey company (Thermotron, Holland, MI) commercially available) in and after 120 hours take out.
Then sample is cut into half inch of wide bar.Then using with the draw rate of 6 inches per minute according to ASTM D6862-04 can be from (the MTS Systems Corporation of Eton, Minnesota State Pu Ruili MTS Systm Corp., Eden Prarie, MN) commercially available " MTSINSIGHT " (10kN development length model) carry out 90 degree and peel off test.Carry out retest and calculate average adhesion values.Result is provided in table 2.
the aging adhesion test result of table 2
Example Aging adhesion test
CE1 72
CE2 97
EX1 >120
EX2 >120
EX3 >120
As used in table 2, greater than flag " > " numerical value afterwards shows, exist the tensile elongation of backing to lose efficacy, but encapsulation piece keeps complete to the adhesion of glass at this numerical value level place at this numerical value place.Thereby, can sum up, aging adhesion test result will be at least up to the described numerical value after described greater than flag, and likely higher than described numerical value.By contrast, odd number (for example, CE1 and CE2 72 and 97) shows, the adhesion between glass and encapsulation piece lost efficacy at this accurate numerical value place.Therefore,, than film and the composition of prior art, table 2 shows exemplary film of the present invention and compositions display goes out the adhesion of enhancing.
All lists of references of mentioning herein are all incorporated to way of reference.
Except as otherwise noted, otherwise in all cases, all numerals that are used for explaining characteristic size, quantity and physical characteristic in the present invention and claims are all interpreted as being modified by term " about ".Therefore, unless indicated to the contrary, otherwise the numerical parameter of listing in above-mentioned specification and claims is approximation, and the desirable characteristics that utilizes instruction content disclosed herein to obtain according to those skilled in the art, these approximations can be different.
Unless herein content otherwise explicitly points out, otherwise the singulative using in this specification and the appended claims " ", " one " and " described " are contained the embodiment with plural form.As used in the present invention and appended claims, the implication of term "or" comprises "and/or" in general, unless this content conclusivelys show other implications.
Various embodiments of the present invention and execution mode are disclosed.The disclosed embodiments only provide for illustrating unrestricted object.Above-mentioned execution mode and other execution mode are all in the scope of following claims.One skilled in the art will appreciate that and can put into practice the present invention by embodiment and execution mode outside those embodiment disclosed in this invention and execution mode.One skilled in the art will appreciate that and can under the prerequisite that does not depart from general principle of the present invention, make multiple change to the details of above-described embodiment and execution mode.Should be understood that, the improper restriction of the exemplary embodiment that the present invention is not intended to be illustrated herein and example, these examples and embodiment only provide by way of example, and scope of the present invention is only intended to the restriction of the following claims that illustrated herein.In addition, not departing under the prerequisite of the spirit and scope of the invention, will be apparent to various modification of the present invention and change to those skilled in the art.Therefore, the application's scope should only be determined by following claims.

Claims (48)

1. can be used in a film for photovoltaic solar cell assembly, described film comprises:
There is DSC peak value fusing point and be less than or equal to the first low-crystalline ethylene/alpha olefin copolymer of 50 DEG C;
There is the second low-crystalline ethylene/alpha olefin copolymer that DSC peak value fusing point is greater than 50 DEG C;
Silane; With
One or more crosslinking agents.
2. film according to claim 1, wherein said silane is unsaturated alkoxy silane.
3. according to the film described in any one of claim 1 or 2, wherein said silane is alkyl acrylate TMOS.
4. according to the film described in any one in claim 1-3, wherein said unsaturated alkoxy silane is alkyl acrylate TMOS.
5. according to the film described in any one in claim 1-4, the alpha-olefin part of wherein said ethylene/alpha-olefin copolymer comprises four or more carbon.
6. according to the film described in any one in claim 1-5, wherein said one or more crosslinking agents are the one in hot curing crosslinking agent and photocured cross-linked dose.
7. according to the film described in any one in claim 1-6, wherein said crosslinking agent is hot curing crosslinking agent.
8. according to the film described in any one in claim 1-7, wherein said hot curing crosslinking agent is peroxide.
9. according to the film described in any one in claim 1-8, wherein said low-crystalline ethylene/alpha olefin copolymer is butylene alpha-olefin.
10. according to the film described in any one in claim 1-9, the DSC peak value fusing point of wherein said the first low-crystalline ethylene/alpha olefin copolymer is less than 45 DEG C.
11. according to the film described in any one in claim 1-10, and the DSC peak value fusing point of wherein said the second low-crystalline ethylene/alpha olefin copolymer is greater than 60 DEG C.
12. according to the film described in any one in claim 1-11, and the DSC peak value fusing point of wherein said the second low-crystalline ethylene/alpha olefin copolymer is greater than 70 DEG C.
13. according to the film described in any one in claim 1-12, also comprises auxiliary agent.
14. according to the film described in any one in claim 1-13, also comprises other resin.
15. according to the film described in any one in claim 1-14, and wherein said the first low-crystalline ethylene/alpha olefin copolymer is that butylene alpha-olefin and described the second low-crystalline ethylene/alpha olefin copolymer are octene alpha-olefin.
16. according to the film described in any one in claim 1-15, and wherein said film comprises described the first low-crystalline ethylene/alpha olefin copolymer and the second low-crystalline ethylene/alpha olefin copolymer that are greater than 70 % by weight.
17. according to the film described in any one in claim 1-16, and the gel fraction of wherein said film is less than 20%.
18. according to the film described in any one in claim 1-17, and the gel fraction of wherein said film is less than 5%.
19. according to the film described in any one in claim 1-18, and wherein said film comprises multiple layers.
20. according to the film described in any one in claim 1-19, is wherein being exposed to " 85/85 durability test " described transmission % on average at least 90% in the wave-length coverage at 400-1100nm after 1000 hours.
21. according to the film described in any one in claim 1-20, and the described adhesion of described film is greater than the 100N/cm recording according to 85/85 durability test of 120 hours.
22. according to the film described in any one in claim 1-21, and the shrinkage on wherein said longitudinal direction is less than 10%.
23. 1 kinds can be used in the film of photovoltaic solar cell assembly, and described film comprises:
There is the first polyolefin that DSC peak value fusing point is less than or equal to 50 DEG C;
There is the second polyolefin that DSC peak value fusing point is greater than 50 DEG C;
Silane; With
One or more crosslinking agents;
Wherein be exposed to " 85/85 durability test " described light transmittance on average at least 90% in the wave-length coverage at 400-1100nm after 1000 hours.
24. films according to claim 23, wherein said the first polyolefin and the second polyolefinic at least one are ethylene/alpha-olefin copolymer.
25. according to the film described in any one of claim 23 or 24, and wherein said the first polyolefin or the second polyolefinic at least one are low-crystalline ethylene/alpha olefin copolymer.
26. according to the film described in any one of claim 24 or 25, and the alpha-olefin part of wherein said ethylene/alpha-olefin copolymer comprises four or more carbon.
27. according to the film described in any one in claim 23-26, and wherein said silane is unsaturated alkoxy silane.
28. according to the film described in any one in claim 23-27, and wherein said silane is alkyl acrylate TMOS.
29. according to the film described in any one in claim 23-28, and wherein said unsaturated alkoxy silane is alkyl acrylate TMOS.
30. according to the film described in any one in claim 23-29, and wherein said one or more crosslinking agents are the one in hot curing crosslinking agent and photocured cross-linked dose.
31. according to the film described in any one in claim 23-30, and wherein said crosslinking agent is hot curing crosslinking agent.
32. according to the film described in any one in claim 23-31, and wherein said hot curing crosslinking agent is peroxide.
33. according to the film described in any one in claim 23-32, and wherein said the first polyolefin and the second polyolefinic at least one are butylene alpha-olefin.
34. according to the film described in any one in claim 23-33, and wherein said the first polyolefinic DSC peak value fusing point is less than 45 DEG C.
35. according to the film described in any one in claim 23-34, and wherein said the second polyolefinic DSC peak value fusing point is greater than 60 DEG C.
36. according to the film described in any one in claim 23-35, and the DSC peak value fusing point of wherein said the second low-crystalline ethylene/alpha olefin copolymer is greater than 70 DEG C.
37. according to the film described in any one in claim 23-36, also comprises auxiliary agent.
38. according to the film described in any one in claim 23-37, also comprises other resin.
39. according to the film described in any one in claim 23-38, and wherein said the first low-crystalline ethylene/alpha olefin copolymer is that butylene alpha-olefin and described the second low-crystalline ethylene/alpha olefin copolymer are octene alpha-olefin.
40. according to the film described in any one in claim 23-39, and wherein said film comprises described the first low-crystalline ethylene/alpha olefin copolymer and the second low-crystalline ethylene/alpha olefin copolymer that are greater than 70 % by weight.
41. according to the film described in any one in claim 23-40, and the gel fraction of wherein said film is less than 20%.
42. according to the film described in any one in claim 23-41, and the gel fraction of wherein said film is less than 5%.
43. according to the film described in any one in claim 23-42, and wherein said film comprises multiple layers.
44. according to the film described in any one in claim 23-43, is wherein being exposed to " 85/85 durability test " described transmission % on average at least 90% in the wave-length coverage at 400-1100nm after 1000 hours.
45. according to the film described in any one in claim 23-44, and the described adhesion of described film is greater than the 100N/cm recording according to 85/85 durability test of 120 hours.
46. according to the film described in any one in claim 23-45, and the shrinkage on wherein said longitudinal direction is less than 10%.
47. according to the film described in any one in claim 1-22, and it is in solar module.
48. according to the film described in any one in claim 23-46, and it is in solar module.
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